KR20160150143A - Preparing method of styrene using oxygen, carbon dioxide and water through dehydrogenation of ethylbenzene - Google Patents
Preparing method of styrene using oxygen, carbon dioxide and water through dehydrogenation of ethylbenzene Download PDFInfo
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- KR20160150143A KR20160150143A KR1020150086462A KR20150086462A KR20160150143A KR 20160150143 A KR20160150143 A KR 20160150143A KR 1020150086462 A KR1020150086462 A KR 1020150086462A KR 20150086462 A KR20150086462 A KR 20150086462A KR 20160150143 A KR20160150143 A KR 20160150143A
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- ethylbenzene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
- C07C15/42—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic
- C07C15/44—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic the hydrocarbon substituent containing a carbon-to-carbon double bond
- C07C15/46—Styrene; Ring-alkylated styrenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
- C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
- C07C5/41—Catalytic processes
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- Engineering & Computer Science (AREA)
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Abstract
Description
TECHNICAL FIELD The present invention relates to a technique for producing a styrene monomer through dehydrogenation of ethylbenzene, and more particularly, to a technique for improving the selectivity and stability of styrene by using carbon dioxide as an oxidizing agent and adding oxygen and water.
Styrene is one of the most important aromatic monomers because it is a necessary element to synthesize a large number of plastics, rubbers, and resins. As demand increases, the consumption and production of styrene are increasing every year.
The commercial production process of most of the styrene is (1) the ethylbenzene adiabatic dehydrogenation process reaction applied by ABIBummus / UOP with the so-called conventional SMTM process, (2) SIMPO process of the cell, (3) pyrolysis gasoline (STEX), and (4) Lurgi's dehydrogenation process of isothermal ethylbenzene.
Direct dehydrogenation in styrene production has the disadvantage that it consumes high energy due to endothermic reaction due to a large amount of vapor, and the catalyst used is sensitive to inactivation because it forms coke. On the other hand, Oxidative Dehydrogenation (ODH) can solve this problem and has unlimited equilibrium, low energy cost, limitation of excessive steam use, and high conversion rate, but it is not commercialized due to the problems of catalyst performance and stability Respectively.
In order to solve the above problems, it has been found that when oxygen is flowed in the oxidative dehydrogenation reaction of propane and butane as oxygen, it accelerates the decomposition of coke by the catalyst, thereby prolonging the catalyst life and increasing the selectivity and activity It is reported that it can be. The process has unlimited equilibrium, low energy cost, limited use of excess steam, and high conversion rate.
In Lummus / UOP's Advanced Styrene Monomer Advanced Reheat Technology (SMART), the traditional steam-reheating process is reheated by selective partial oxidation of the reactants remaining in the dehydrogenation catalyst (see patent document 1). The reaction takes place in a catalyst having high selectivity in the presence of air or oxygen, exhibiting a conversion in the range of 77 to 93% and a selectivity of 92 to 96%. At this time, the exothermic oxidation reaction of oxygen and hydrogen provides some necessary heat to the dehydrogenation reaction of ethylbenzene, and the removal of hydrogen in the above process shifts the reaction equilibrium so that the conversion of ethylbenzene into single- Allowing the selectivity of high styrene monomers to be maintained. However, in order to use the above process, it is necessary to solve the problems of increasing the capacity of the reaction, increasing the yield of the product, minimizing undesired products, and replacing expensive equipment.
Other Styro-Plus processes have advantages such as high conversion rate, high styrene selectivity, reduced steam requirement, and low temperature reactor, but the use of two catalysts in the reactor, complex reactor design, There is a risk that the reactor will explode due to explosive heat generation which is a severe side reaction due to complete oxidation of oxygen.
Recently, Lummus et al. Have disclosed a process for producing styrene monomers by oxidative dehydrogenation of ethylbenzene using carbon dioxide as a soft oxidant (see Patent Document 2). In this technique, ethylbenzene is converted to styrene by catalytic dehydrogenation under carbon dioxide and a small amount of steam in a single or batch fixed bed catalytic reactor connected in series with reheating.
What is important in the oxidative reheating step is a catalyst for selectively oxidizing only hydrogen. The performance of the oxidation catalyst is to reheat without any inhibitor or toxicity, and it is important for the dehydrogenation process using oxygen to have a selectivity of high styrene of at least 90%.
Recently, it has been reported that an extremely stable homogeneous mesoporous carbon catalyst obtained 74% ethylbenzene conversion and 62% styrene selectivity at 350 ° C (see Non-Patent Document 1).
In addition, the application of carbon dioxide as a diluent slows down the selectivity of styrene and the reduction of catalytic activity by the coupling reaction between dehydrogenation reaction and reverse water gas shift reaction, reduction of ethylbenzene, reduction of coke formation, selectivity of styrene .
In particular, the new process using carbon dioxide has a latent heat of condensation, so the dehydrogenation reaction in the presence of carbon dioxide can be an energy saving process because the energy required is less than the current process.
Zirconia is very important in terms of catalytic reaction because it exhibits normal surface area, reduction-oxidation ability by acid-base function, and high thermal stability. Although the dehydrogenation reaction of ethylbenzene with zirconia showed a conversion of ethylbenzene of 60% and selectivity of styrene monomer of 90%, it was found that even after 10 hours of reaction, the activity decreased by 15% Only.
For the dehydrogenation of ethylbenzene under carbon dioxide, a catalyst in which transition metal oxides of Ti, Mn or Sn based on zirconia are mixed has been developed. The binary metal oxides have an improved surface area with amorphousness and a large number of intermediate-acid acid-base points, and the conversion of ethylbenzene to ethylbenzene to styrene using carbon dioxide, a soft oxidant, Selectivity.
As a result, various studies have been carried out to increase the conversion of ethylbenzene and the selectivity of styrene in the dehydrogenation process of ethylbenzene using carbon dioxide as an oxidizing agent. However, studies on suitable conditions for producing high yield styrene Do.
Accordingly, it is an object of the present invention to provide a method for producing styrene monomers for producing styrene from ethylbenzene using a dehydrogenation process in which oxygen is supplied to an amphoteric catalyst and carbon dioxide containing water is added.
In order to accomplish the above object, the present invention provides a method for producing a catalyst for olefin polymerization, comprising: (a) a step of flowing ethylbenzene together with at least one member selected from the group consisting of carbon dioxide and water into an amphoteric catalyst; And a step of injecting oxygen into the amphoteric catalyst of the first step to produce a styrene monomer by converting the ethylbenzene through a dehydrogenation reaction (second step).
The method for producing styrene according to the present invention comprises the steps of supplying carbon dioxide as a mild oxidizing agent to promote the oxidative dehydrogenation reaction of ethylbenzene and supplying water together to remove coke from the surface caused by the sweeping process of the catalyst, It has an effect of suppressing the cracking of ethylbenzene and improving the catalytic activity by improving the carbon dioxide surface adsorption ability on the catalyst surface through the interaction of carbon dioxide and water. In addition, oxygen is supplied to oxidize the coke formed on the surface (exothermic reaction) to remove it.
Therefore, the styrene production method according to the present invention has an effect of increasing the catalytic activity and stability through the double functional function of acid-base on the surface of the catalyst, the suppression of coke by moisture, and the removal of coke by oxygen.
Hereinafter, embodiments of the present invention will be described in detail.
The inventors of the present invention have been studying a suitable condition for producing high yield styrene in the dehydrogenation process of ethylbenzene using carbon dioxide as the oxidizing agent. In the process of supplying oxygen to the amphoteric catalyst and adding carbon dioxide containing water It has been confirmed that a high yield of styrene can be prepared from ethylbenzene by the dehydrogenation process, thereby completing the present invention.
The production method of the citene is a step (first step) of flowing ethylbenzene together with at least one selected from the group consisting of carbon dioxide and moisture to the amphoteric catalyst; And injecting oxygen into the amphoteric catalyst of the first step to produce a styrene monomer by converting the ethylbenzene through a dehydrogenation reaction (second step).
The method for preparing styrene may further include a pretreatment step for preparing an amphoteric catalyst by pretreating the metal oxide before the first step. At this time, the metal oxide in the pretreatment step may include at least one selected from the group consisting of titania, zirconia, an alkali metal, and an alkaline earth metal.
The method for preparing styrene may further include the step of vaporizing ethyl benzene before the first step. For example, in the first step, ethylbenzene may be fed to the amphoteric catalyst together with carbon dioxide or together with carbon dioxide and moisture in the vaporized state.
The ethylbenzene is supplied as a raw material for producing the styrene monomer, and the carbon dioxide is supplied as a soft oxidizing agent during the reaction to promote the oxidative dehydrogenation reaction of ethylbenzene. At this time, water is supplied together to remove the surface coke caused by the sweeping process of the catalyst, to suppress the cracking of ethylbenzene, and to enhance the carbon dioxide surface adsorption ability on the catalyst surface through the interaction of carbon dioxide and water The catalyst has an effect of improving the activity, and the supplied oxygen serves to oxidize (exothermic) the coke formed on the surface and remove the coke. Therefore, the catalytic activity and stability can be increased by the double functional group of the acid-base on the surface of the catalyst, the suppression of coke by moisture, and the removal of coke by oxygen.
Ethylbenzene is converted to a styrene monomer through an oxidative dehydrogenation reaction by two parallel reactions as shown in the following Reaction Schemes 1 and 2:
<Reaction Scheme 1>
Ethyl benzene → Styrene + H 2
<Reaction Scheme 2>
Ethyl benzene + CO 2 → Styrene + CO + H 2 O
In this case, Reaction Scheme 2 may be a combination of the two reactions of Reaction Scheme 3:
<Reaction Scheme 3>
(1) Ethyl benzene → Styrene + H 2
(2) H 2 + CO 2 → CO + H 2 O
Reaction (1) in the above reaction scheme 3 is an endothermic reaction in the conventional ethylbenzene dehydrogenation reaction, and reaction (2) is an exothermic reaction in a mild oxidation reaction of hydrogen. The reaction (2) is used to remove by-product hydrogen from the reaction gas mixture, which advantageously alters the equilibrium conversion of the main ethylbenzene dehydrogenation reaction (1). Further, the exothermic reaction (2) provides a part of the heat required for the endothermic reaction (1).
Wherein the alkali metal is one or more selected from the group consisting of lithium (Li), potassium (K), sodium (Na) and ruthenium (Ru), and the alkaline earth metal is at least one selected from the group consisting of magnesium (Mg), calcium (Ca) , Lanthanum (La), praseodymium (Pr), and cerium (Ce), but are not limited thereto.
When an alkali metal or alkaline earth metal is doped in an oxide catalyst such as titania, zirconia or a mixture thereof, the alkali metal acts as an active component in the catalyst, neutralizing the active sites and generating base points. In addition, it can act as an electronic factor, lowering the melting point of the liquid phase in the supported liquid catalyst, preventing phase shift and being used as an auxiliary material in catalyst preparation and preventing the active component from volatilization .
The pretreatment of the amphoteric catalyst in the pretreatment step is carried out, for example, at a temperature of 500 to 700 ° C for 20 to 60 minutes under a nitrogen flow of 10 to 30 ml / min. The ethylbenzene is vaporized by applying heat at 120 to 140 ° C .
The molar ratio of carbon dioxide to ethylbenzene in the first step is preferably 0.5 to 30. If carbon dioxide is supplied at a molar ratio of less than 0.5 with respect to ethylbenzene, the contact time with respect to the surface of the catalyst becomes long, thereby cracking and coking may occur. When the molar ratio exceeds 30, The gas hourly space velocity (GHSV) of the gas is increased, so that the contact time of the supplied reaction gas on the catalyst surface is shortened and the yield of styrene decreases.
The molar ratio of water to ethylbenzene in the first step is preferably 0.01 to 5. When water is supplied at a rate of less than 0.01 mol based on the amount of ethylbenzene, a small amount of water is supplied to remove the coke formed on the surface of the catalyst and inhibit the cracking of ethylbenzene, And when moisture is supplied in excess of 5 molar ratio with respect to ethylbenzene, there is a problem that deformation may occur on the catalyst due to excessive water supply.
The moisture may be supplied through one or more methods selected from the group consisting of a syringe pump injection method, a pulse spraying method, and a vaporizing method together with a carbon dioxide gas bubble.
The molar ratio of oxygen to ethylbenzene in the second step is preferably 0.0001 to 0.05. If the temperature is outside the above range, the formation of coke due to ethylbenzene may increase, which may cause problems.
In addition, the oxygen in the second step may be injected in a pulsed or continuous manner.
In the second step, the dehydrogenation reaction is preferably carried out under the conditions of a pressure range of 0.01 to 10 atm, a liquid hourly space velocity (LHSV) of 0.1 to 100 h -1 , and a reaction temperature of 400 to 650 ° C . If the reaction conditions are out of the range, the conversion efficiency of ethylbenzene and the yield of styrene are lowered. Particularly, when the reaction is carried out at a pressure of less than 0.01 atm, the contact time of the catalyst is shortened, and when the pressure is higher than 10 atm, the yield of styrene is lowered.
Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
≪ Example 1 >
1.0 g of Na-TZ was attached to a stainless steel reactor having an inner diameter of 4.5 mm and a length of 300 mm at normal pressure, and a quartz cotton was attached to the top and bottom of the catalyst. Prior to the reaction, the catalyst was pretreated at 600 ° C for 30 minutes under a nitrogen flow of 20 ml / min. After the pretreatment, ethylbenzene vaporized at 120 ° C was flowed into the catalyst at a rate of 8.2 mmol / h in the course of carbon dioxide or carbon dioxide / water, and oxygen was continuously injected or 5 ml of oxygen was injected every 30 minutes. Comparative Control 1 of Table 1 below maintained the molar ratio of 1 ethylbenzene: 5.1 carbon dioxide. Comparative Control 2 in Table 1 maintained the molar ratio of 1 ethylbenzene: 5.1 carbon dioxide: 0.042 water. Comparative control group 3 in the following Table 1 was pulse-injected with oxygen at a molar ratio of 1 ethylbenzene: 5.1 carbon dioxide: 0.042 moisture: 2.0 x 10 -4 oxygen (pulse injection) every 30 minutes. The product was analyzed using a gas chromatogram equipped with a thermal conductivity detector (TCD) and a flame ionization detector (FID) (Younglin Instrument, Acme 6000). The conversion of ethylbenzene (EB X,%) and the selectivity of styrene (Sel.,%) Were calculated as shown in the following Equation 1, and the results are shown in Table 1 below.
&Quot; (1) "
Ethylbenzene conversion rate (%) = [(A-B) / A] 100
Styrene selectivity (%) = [C / (A-B)] x 100
Wherein A is the concentration (% by weight) of the injected ethylbenzene, B is the concentration (% by weight) of residual ethylbenzene after the reaction, and C is the concentration (% by weight)
As shown in Table 1, it was confirmed that the conversion of ethylbenzene was high when carbon dioxide and water were fed at 10 hours, but the conversion of ethylbenzene was excellent when carbon dioxide, water and oxygen were simultaneously fed at 24 hours.
≪ Example 2 >
In Example 2, the molar ratio of ethylbenzene to carbon dioxide was in accordance with the conditions of Example 1, and oxygen pulse injection was gradually increased at a predetermined time during the continuous reaction of the catalyst. The conversion (EB X,%) of ethylbenzene thus obtained and the selectivity (Sel.,%) Of styrene are shown in Table 2 below. 0.2 mmol of oxygen was injected into the Na-TZ catalyst for 3 hours every 30 minutes and 0.4 mmol of oxygen was injected every 30 minutes for 4 hours. Then, 0.6 mmol of oxygen was injected every 30 minutes for 3 hours.
As shown in Table 2 above, EB X (%) and Sel. (%) Increased in the first year.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that such detail is solved by the person skilled in the art without departing from the scope of the invention. will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (12)
Injecting oxygen into the amphoteric catalyst of the first step to produce a styrene monomer by converting the ethylbenzene through a dehydrogenation reaction (second step)
≪ / RTI >
A pretreatment step of pretreating the metal oxide before the first step to produce the amphoteric catalyst
≪ / RTI >
Wherein the metal oxide comprises at least one selected from the group consisting of titania, zirconia, an alkali metal, and an alkaline earth metal.
Wherein the alkali metal is at least one selected from the group consisting of lithium (Li), potassium (K), sodium (Na), and ruthenium (Ru).
Wherein the alkaline earth metal is at least one selected from the group consisting of magnesium (Mg), calcium (Ca), barium (Ba), lanthanum (La), praseodymium (Pr) and cerium (Ce).
The pre-
And at a temperature of 500 to 700 占 폚 for 20 to 60 minutes at a flow rate of 10 to 30 ml / min.
Vaporizing the ethylbenzene prior to the first step
Further comprising:
In the first step,
Wherein the vaporized ethylbenzene is fed to the amphoteric catalyst together with at least one member selected from the group consisting of carbon dioxide and water.
Wherein the molar ratio of carbon dioxide to ethylbenzene in the first step is 0.5 to 30.
Wherein the molar ratio of water to ethylbenzene in the first step is 0.01 to 5.
Wherein the mole ratio of oxygen to ethylbenzene in the second step is 0.0001 to 0.05.
Wherein oxygen is injected in a pulsed or continuous manner in the second step.
The dehydrogenation reaction in the second step is carried out under the conditions of a pressure range of 0.01 to 10 atm, a liquid hourly space velocity (LHSV) of 0.1 to 100 h -1 , and a reaction temperature of 400 to 650 ° C. Gt;
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4435607A (en) | 1981-04-28 | 1984-03-06 | Uop Inc. | Dehydrogenation of dehydrogenatable hydrocarbons |
| US7964765B2 (en) | 2008-06-14 | 2011-06-21 | Lummus Technology Inc. | Styrene monomer process based on oxidative dehydrogenation of ethylbenzene using CO2 as a soft oxidant |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4435607A (en) | 1981-04-28 | 1984-03-06 | Uop Inc. | Dehydrogenation of dehydrogenatable hydrocarbons |
| US7964765B2 (en) | 2008-06-14 | 2011-06-21 | Lummus Technology Inc. | Styrene monomer process based on oxidative dehydrogenation of ethylbenzene using CO2 as a soft oxidant |
Non-Patent Citations (1)
| Title |
|---|
| 1. Chem. Asian J. 4 (2009) 1108. |
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